Phenolic-resin-modified natural resin acid esters, processes for their preparation and their use in printing inks

Abstract

Phenolic-resin-modified natural resin acid esters obtained by reaction of A) natural resins or natural resin acids, B) mononuclear or polynuclear alkylolizable phenols, C) aldehydes or aldehyde acetals, D) aliphatic, cycloaliphatic or araliphatic polyols, E) magnesium compounds, F) if appropriate, fatty acids or fatty acid compounds and G) if appropriate, ethylenically unsaturated hydrocarbon resins, at a temperature of 100° to 250° C. and subsequent azeotropic removal of the water by distillation by means of an entraining agent at 200° to 300° C.

I claim: 
     
       1. A phenolic-resin-modified natural resin acid ester composition prepared by reacting at least one compound of each of the groups comprising A) 20 to 80% by weight of natural resins or natural acid resins   B) 10 to 45% by weight of mononuclear or polynuclear phenols,   C) 2 to 20% by weight of aldehydes or aldehyde acetals and   D) 1 to 20% by weight of aliphatic, cycloaliphatic or araliphatic alcohols having at least two hydroxyl groups, in the presence of   E) 0.1 to 2% by weight of magnesium compounds calculated as MgO and optionally compounds selected from the groups consisting of   F) fatty acids, fatty oils or fats and   G) ethylenically unsaturated hydrocarbon resins, at temperature of 100° to 250° C. and subsequent azeotropic removal of water by distillation by means of an entraining agent at 200° to 300° C., the weight percentage being based on the total weight of the composition.     
     
     
       2. The resin acid ester composition of claim 1 containing 30 to 75% by weight of group A), 2 to 20% by weight of group C), and 1 to 25% by weight of group G). 
     
     
       3. A process for preparing the phenolic-resin-modified natural resin acid ester composition of claim 1 by reacting 20 to 80% by weight of natural resins or natural resin acids from group A),   10 to 45% by weight of phenolic compounds from group B),   2 to 20% by weight of aldehyde compounds from group C),   or, instead of the compounds from groups B) and C) or as a proportion with the compounds from groups B) and C), condensation products in a phenol-resol form prepared separately from compounds of groups B) and C),   1 to 20% by weight of polyol compounds from group D),   0.01 to 2% by weight, calculated as MgO, of magnesium compounds from group E),   0 to 30% by weight of fatty acid, fatty oils and fats from group F),   0 to 30% by weight of a hydrocarbon resin from group G), together with   0.01 to 20% by weight of an inert entraining agent, the weight percentages based on the total amount of the compounds employed.   
     
     
       4. A binder for printing inks comprising 1 to 99 parts by weight of the resin acid ester compositin of claim 1 and 99 to 1 parts by weight of a mineral oil. 
     
     
       5. The binder of claim 4 also containing an additive selected from the group consisting of colophony, colophony esters, vegetable oils and alkyd resins, phenolic resins, polystyrene and mixtures thereof. 
     
     
       6. A printing ink for offset printing and letter press printing containing as a binder resin the resin acid ester composition of claim 1.